JP2003500194A - Catalyst comprising partially amorphous zeolite Y and its use in hydroconversion of hydrocarbon petroleum feedstocks - Google Patents

Abstract

  (57) [Summary] PROBLEM TO BE SOLVED: To provide a catalyst containing a partially amorphous zeolite Y and its use in hydroconversion of a hydrocarbon petroleum feedstock. SOLUTION: This comprises at least one matrix and at least one partially amorphous zeolite Y having a peak fraction of less than 0.4 and a crystalline portion less than 60% relative to the reference zeolite in sodium form. It is a catalyst. It preferably further contains at least one hydrogenation / dehydrogenation element. The zeolite has an overall Si / Al ratio greater than 15, and an Si / Al ratio greater than or equal to the overall Si / Al ratio.^IVSkeleton ratio, pore volume at least equal to 0.20 ml / g of solid (8-50% of which consists of pores having a diameter of at least 5 nm), and specific surface area of 210-800 m ²/ G.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention is directed to at least one matrix, partially amorphous zeolite Y, and optionally at least one hydrogenated / dehydrogenated metal selected from the group consisting of Group VIB and Group VIII metals of the Periodic Table. And a catalyst optionally comprising at least one element selected from the group consisting of phosphorus, boron and silicon, optionally at least one element of group VIIA and optionally at least one element of group VIIB Regarding The invention also relates to a hydroconversion of a hydrocarbon feed,
Use of the catalyst for obtaining high viscosity oils, especially in hydrocracking, and very particularly with a viscosity index (VI) of greater than 95-100, preferably 95-150, more particularly 120-140. Also related to.

[0002]   The catalyst may be used in the hydrorefining of hydrocarbon feeds.

[0003]

[Prior art]

Hydrocracking of heavy petroleum fractions begins with excess heavy feedstocks that cannot be easily improved, such as gasoline, jet fuel and light gas oils, where refiners are required to adapt their production to the demand structure. It is a very important purification method that enables the production of even lighter fractions. It is also possible by some hydrocracking methods to obtain highly refined residues which can constitute a good oil base. The advantage of catalytic hydrocracking over catalytic cracking is that it provides very good quality middle distillates, jet fuels and gas oils. The gasoline produced has a much lower octane number than the gasoline obtained by catalytic cracking.

The catalyst used in hydrocracking is a bifunctional catalyst that combines an acid function and a hydrogenation function. The acid function is a large specific surface area (generally 150 to 800 m) with halogenated alumina (especially chlorinated or fluorinated alumina), a combination of boron oxides and aluminum oxides, amorphous silica-alumina, and zeolites. ² / g) of the carrier. The hydrogenation function is
By one or several metals from Group VIII of the Periodic Table or VI of the Periodic Table
It is provided by a combination of at least one Group B metal and at least one Group VIII metal.

The equilibrium between the two functions, acid and hydrogenation, is a fundamental parameter that regulates the activity and selectivity of the catalyst. Due to its weak acid function and strong hydrogenation function, it is not very active and is generally at high temperature (above 390 ° C.) and at low feed space velocity (VVH expressed by the volume of feed to be treated per unit of catalyst volume per hour is It generally operates at 2 h ⁻¹ or less), but provides very good selectivity for middle distillates. Conversely, the strong acid and weak hydrogenation functions provide catalysts that are active but have less favorable selectivity for middle distillates. Thus, the search for suitable catalysts focuses on the judicious selection of each of the functions to tune the activity / selectivity pair of catalysts.

Therefore, one of the major advantages of hydrocracking is that it exhibits great flexibility at different levels: ie with regard to the catalyst used, which is obtained thereby. With regard to the substance, it provides the adaptability of the feedstock to be treated. A simple parameter to adjust is the acidity of the catalyst support.

Conventional catalytic hydrocracking catalysts consist in the majority of weakly acidic supports such as, for example, amorphous silica-alumina. These systems are used more particularly for producing very good quality middle distillates and, if their activity is very weak, oil bases.

The family of amorphous silica-alumina is found in weakly acidic supports. Many catalysts in the hydrocracking market are combined with Group VIII metals or, preferably, when the heteroatom content of the feed to be treated exceeds 0.5% by weight,
It has a base of silica-alumina in combination with a sulphide of a Group VIB metal and a Group VIII metal. These systems have very good selectivity in middle distillates and the products produced have excellent quality. These catalysts are also capable of producing lubricating base oils with less acidic ones of the catalysts. The drawback of all these catalyst systems using amorphous support bases is their weak activity, as said.

Catalysts containing FAU-structured zeolite Y or beta-type catalysts have higher catalytic activity than amorphous silica-alumina catalysts, but higher selectivity for light materials.

Hydrotreating is increasing in refinery practice with a great need to reduce the amount of sulfur in petroleum fractions and convert heavy fractions into lighter fractions that can be fueled and improved. Cause importance. This creates, on the one hand, an increasing demand for fuels that are required to convert an increasing number of imported crude oils into heavy fractions and heteroatoms containing nitrogen and sulfur, and on the other hand, for commercial fuels. Standards are imposed on the content of sulfur and aromatics in various countries of the world. This improvement in quality is accompanied by a relatively significant reduction in the molecular weight of the heavy components. This may be obtained, for example, using a cracking reaction.

In current catalytic hydrorefining processes, the main reactions that help to use the heavy fraction,
Especially hydrogenation of aromatic nuclei (HAR), hydrodesulfurization (HDS), hydrodenitrification (HDN)
And other catalysts that can facilitate dehydrogenation are used. Hydrorefining is used to treat feedstocks such as gasoline, gas oils, vacuum gas oils, deasphalted or non-asphalted residues under atmospheric or vacuum conditions. For example, cracking and catalytic hydrocracking processes are shown for pretreatment of feedstocks. The nitrogen-containing heterocyclic compounds present in the heavy fraction act as poisons with very significant toxicity for cracking or hydrocracking catalysts.

Consequently, denitrification of catalytic hydrocracking feedstocks constitutes one of the possible means to improve the overall yield of these processes. Therefore, it is desirable to reduce the nitrogen content of the feedstock as much as possible before cracking the feedstock. At least one hydrorefining step is usually integrated with known methods for upgrading heavy petroleum fractions.

In the prior art, the zeolites used for the preparation of hydrocracking catalysts have a SiO ₂ / Al ₂ O ₃ framework molar ratio, their crystal parameters, their pore distribution,
It is characterized by several parameters such as its specific surface area, its sodium ion adsorption capacity or else its water vapor adsorption capacity. Therefore, the above-mentioned patents of the applicant (French patent applications FR-A-2754742 and FR-A-2754).
826), crystal parameters 24.15 to 24.38Å (1Å = 0.1 nm).
, SiO ₂ / Al ₂ O ₃ skeleton molar ratio 500-21, sodium content less than 0.15% by weight, sodium ion adsorption capacity over 0.85 g sodium / 100 g zeolite, specific surface area over 400 m ² / g, 6% Zeolites having a water vapor adsorption capacity of more than 1 and a pore volume of 1 to 20% contained in pores having a diameter of 20 to 80 liters are used.

[0014] US Pat. No. 4,857,170 describes the use of modified zeolites in the hydrocracking with crystallization parameters below 24.35Å.
However, it has no effect from the modification treatment on its crystallinity.

Moreover, these prior arts show that there has always been an effort to maintain a crystalline fraction (or crystallinity) and a high peak fraction in the zeolites used. On the contrary, due to the exploratory work carried out by the Applicant on a large number of zeolites and microporous solids, contrary to this, at least one partially crystallized, FAU-structured zeolite Y is selected. It has been found that the containing catalysts are capable of achieving a markedly improved middle distillate (kerosene and gas oil) selectivity over catalysts containing zeolite Y known in the prior art.

[0016] In addition, by the same achievements as above, it is quite unexpected by the Applicant that zeolite Y samples modified in a different way have the same characteristics as those cited in the prior art or those It was noted that it has a feature very close to, but in contrast, is capable of exhibiting different peak proportions and different crystalline moieties and has different reactivities.

[0017]

[Constitution of the invention]

More specifically, the present invention is directed to a catalyst comprising at least one matrix and optionally at least one element selected from the group consisting of Group VIII and Group VIB elements, whereby It is characterized in that the catalyst contains partially amorphous zeolite Y.

The partially amorphous zeolite Y used in the present invention has a peak ratio of i / 0.40, preferably less than about 0.30 and ii / less than about 60%, preferably less than about 50%. With a crystalline portion displayed against the reference zeolite Y in the sodium (Na) form.

The solid, which is a partially amorphous zeolite Y which is preferably part of the composition of the catalyst according to the invention, has the following other characteristics: iii / 15, preferably more than 20 and less than 150 overall Si / Al
Ratio, iv / Si / Al ^iv skeleton ratio that is greater than or equal to the total Si / Al ratio, and v / pore volume that is at least equal to 0.20 ml / g of solids (8-50% of which is at least 5 nm and m) that is from pores having a ^{50Å), vi / 210~800m 2 /} g, preferably 250~750m ² / g, preferably at least one of the specific surface area of 300 to 600 m ² / g (Preferably all) features.

The peak percentages and crystalline fractions are according to ASTM D3906-97 method “Determinati
on of Relative X-ray Diffraction Intensities of Faujasite-Type-Containin
g Materials (measurement of the relative X-ray diffraction intensities of faujasite-type contained materials) ”, using a procedure based on X-ray diffraction. It is possible to refer to this method for the preparation.

The diffractogram consists of spectral lines characteristic of the sample and the crystallized portion of the bottom of the hole, which are essentially produced by the distribution of the amorphous or microcrystalline portion of the sample (weak dispersion signal is Related to equipment, air, sample holders, etc.). The peak fraction of zeolites is defined as the total area of the diffractogram (peak + peak + θ + 2θ, 1 = 0.154 nm when copper Kα radiation is used), which is predefined.
It is the ratio of the area of the spectrum line (peak) of zeolite to the valley (trough). This peak / (peak + valley) ratio is proportional to the amount of crystallized zeolite in the material.

In order to calculate the crystalline portion of the zeolite Y sample, the peak ratio of the sample is 10
It is compared to the peak percentage of a reference (eg NaY) which is considered to be 0% crystallized. The peak ratio of completely crystallized Na zeolite Y is 0.55 to 0.
It is about 60.

The peak ratio of standard zeolite USY is 0.45 to 0.55. Its crystalline fraction for fully crystallized NaY is 80-95%. The peak proportion of the solids which is the subject of the present invention is less than 0.4, preferably less than 0.35. Therefore, its crystalline portion is less than 70%, preferably less than 60%.

Partially amorphous zeolites are generally prepared according to the techniques used for dealumination, starting from the commercially available zeolite Y, which has a high crystallinity (at least 80%). More generally, it is possible to start with a zeolite having at least 60% or at least 70% crystalline fraction.

Zeolite Y, commonly used in hydrocracking catalysts, is produced by modifying commercially available Na-zeolite Y. This modification makes it possible to make so-called stabilized zeolites, ultra-stabilized zeolites or other dealuminated zeolites. This modification is carried out by at least one of the dealumination techniques, for example hydrothermal treatment, acid attack.

Preferably, this modification is carried out by a combination of three types of operations known to those skilled in the art: a combination of hydrothermal treatment, ion exchange and acid attack. Hydrothermal treatment is preferably fully defined by a combination of variable operations such as temperature, duration, total pressure and partial pressure of steam. This treatment has the effect of extracting the silica-alumina skeleton of the zeolite from the aluminum atoms. As a result of this processing, S
An increase in the iO ₂ / Al ₂ O ₃ skeleton molar ratio and a decrease in the parameters of the crystal network occur.

Ion exchange is generally carried out by immersing the zeolite in an aqueous solution containing ions that can be fixed to the cation exchange sites of the zeolite. The sodium cations present in the zeolite after crystallization are also removed.

The acid attack procedure consists of contacting the zeolite with an aqueous solution of an inorganic acid. The severity of acid attack is regulated by acid concentration, duration and temperature. This process
By being carried out on zeolites which are treated hydrothermally, it has the effect of removing the aluminum radicals that are drawn from the framework and occlude solid micropores.

The partially amorphous zeolite Y used in the catalyst according to the present invention is at least partially hydrogen type, acid (H ⁺ ) type, ammonium (NH ₄ ⁺ ) type or cationic form. Thereby, the cations are group IA, group IB, IIA.
Group B, Group IIB, Group IIIA, Group IIIB (including rare earths), Sn, Pb and Si. It is preferably at least partly in the H ⁺ (hydrogen) form. It may be used in at least partially cationic form (as defined above).

Partially amorphous zeolite Y, which is at least partly in acid form (preferably H form as a whole) or which is partly exchanged with cations such as, for example, alkali cations and / or alkaline earth cations, is preferred. Is used.

The catalyst comprising at least one partially amorphous zeolite Y also comprises a hydrogenation function.
The hydrogenation function is preferably defined in groups VIB and VII of the periodic table as defined above.
It contains at least one metal selected from the group consisting of Group I metals.

The catalyst of the present invention may comprise at least one noble metal element or non-noble metal element of Group VIII such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. As Group VIII metals it is preferred to use non-metals such as iron, cobalt and nickel. The catalyst according to the invention may comprise at least one element from group VIB, preferably tungsten and molybdenum. The following metal combinations are preferably used: nickel molybdenum, cobalt molybdenum, iron molybdenum, iron tungsten, nickel tungsten and cobalt tungsten. A preferred combination is nickel molybdenum, cobalt molybdenum and nickel tungsten. It is also possible to use combinations of three metals, for example nickel-cobalt-molybdenum.

The catalyst of the present invention also comprises at least one amorphous or partially crystallized porous inorganic matrix of the oxide type. Non-limiting examples include alumina, silica and silica-alumina. It is also possible to select an aluminate. It is preferred to use matrices containing alumina in all of these forms known to those skilled in the art, and even more preferably alumina, such as gamma alumina.

In an embodiment of the present invention, the catalyst preferably comprises at least one element selected from the group consisting of boron, silicon and phosphorus. The catalyst comprises at least one element of Group VIIA, preferably chlorine and fluorine, and optionally at least one element of Group VIIB.

The boron, silicon and / or phosphorus may be in the matrix and in the zeolite, or is preferably supported on the catalyst and then mainly localized on the matrix.

The introduced elements, in particular the silicon, which is mainly localized on the matrix of the support, are of the transmission type linked to Castaing's microprobes (distribution curves of various elements) and to the X-ray analysis of the components of the catalyst. It can be characterized by techniques such as electron microscopy, or else by the establishment of methods of creating a distribution of the elements present in the catalyst by electron microprobes.

The catalysts of the present invention are generally present in wt% relative to the total weight of the catalyst as follows: at least one hydrogenated / dehydrogenated metal 0, preferably selected from the group consisting of Group VIB and Group VIII metals. 60%, advantageously 0.1-60%, preferably 0
． 1-50%, even more preferably 0.1-40%, at least one oxide-type amorphous or incompletely crystallized porous inorganic matrix 0.1-99.9%, preferably 0.1. 1- (99.8% or 99.7% or 99.6% or 99%), preferably 1-98%, wherein the catalyst is partially amorphous zeolite Y 0.1-99.9%, Preferably 0.1-
99.8% or 99%, more preferably 0.1-90%, even more preferably 0.1-80%, whereby the catalyst optionally comprises: silicon, boron and phosphorus, preferably At least one promoter element selected from the group consisting of boron and / or silicon 0 to 20%, preferably 0.1 to 15
%, Even more preferably 0.1 to 10%, at least one element selected from Group VIIA, preferably fluorine 0 to 20%,
Preferably 0.1 to 15%, even more preferably 0.1 to 10%, at least one element selected from Group VIIB 0 to 20%, preferably 0.1 to
15%, and even more preferably 0.1 to 10%.

The Group VIB, Group VIII and Group VIIB metals of the catalyst of the present invention may be present in all or part of the metal and / or oxide and / or sulfide form.

The catalyst may be prepared by any method known to those skilled in the art. that is,
It is preferably obtained by kneading the matrix and zeolite, and the kneaded product is then shaped. The hydrogenating element is introduced during kneading or preferably after shaping. Firing is performed after molding. The hydrogenating element is then introduced either before or after this calcination. The preparation ends with firing at a temperature of 250-600 ° C. One of the preferred methods according to the present invention is to knead partially amorphous zeolite Y powder in wet alumina gel for several tens of minutes, and the paste thus obtained has a diameter of 0.4-4.
It consists of passing through a die to form mm extrudates.

The hydrogenation function is only partially (for example, in the case of a combination of Group VIB and Group VIII metal oxides) when the zeolite or partially amorphous zeolite Y is mixed with the oxide gel selected as the matrix. It may be introduced or all of them may be introduced.

The hydrogenation function may be carried out once or several times on a calcined support consisting of partially amorphous zeolites dispersed in a selected matrix using a solution containing a precursor salt of the selected metal. It may be introduced by an ion exchange operation.

The hydrogenation function is shaped and calcined by a solution containing at least one precursor of at least one oxide of at least one metal selected from the group consisting of Group VIII metals and Group VIB metals. The carrier may be introduced by one or more impregnation operations. Thereby, a precursor of at least one oxide of at least one metal of group VIII is preferably introduced after the precursor of group VIB, or the catalyst is combined with at least one metal of group VIB. , At least one Group VIII metal, the precursor is introduced simultaneously with the Group VIB precursor.

If the catalyst comprises at least one element of group VIB, for example molybdenum, for example, the catalyst is impregnated with a solution comprising at least one element of group VIB, it is dried and then It is possible to bake it. Molybdenum impregnation
It may be promoted by adding phosphoric acid in a solution of ammonium paramolybdate, which also makes it possible to introduce phosphorus which promotes catalytic activity.

In a preferred embodiment of the present invention, the catalyst comprises as promoter a at least one element selected from silicon, boron and phosphorus. These elements include at least one partially amorphous zeolite Y and at least 1 part, as defined above.
One matrix and at least one metal selected from the group consisting of Group VIB and Group VIII metals.

The catalyst comprises a group of boron, silicon, phosphorus, and optionally halide ions.
An element selected from group VIIA and optionally at least one selected from group VIIB
When including two elements, these elements may be introduced into the catalyst in different ways at different levels of preparation.

Impregnation of the matrix is preferably carried out by the so-called “dry” impregnation method known to the person skilled in the art. Impregnation may be done in a single step with a solution containing all of the components of the final catalyst.

The element selected from P, B, Si and Group VIIA halide ions may be introduced by one or more impregnation operations with excess solution on the calcined precursor.

When the catalyst comprises boron, the preferred process according to the invention is the use of at least one borate such as ammonium viborate or ammonium pentaborate in alkaline medium in the presence of oxygen-containing water. It consists of preparing an aqueous solution and starting with so-called dry impregnation. In the dry impregnation, the pore volume of the precursor is filled with a solution containing boron.

When the catalyst contains silicon, a solution of silicone type silicon compound is used.

When the catalyst comprises boron and silicon, the loading of boron and silicon may be done simultaneously with a solution containing a boron salt and a silicone type silicon compound.

Thus, for example, if the precursor is a nickel-molybdenum-type catalyst supported on a support containing partially amorphous zeolite Y and alumina, the precursor may be combined with ammonium viborate and Rhone-Poulin. Impregnated with an aqueous solution of Rhodorsil E1P silicone of the company, drying is started eg at 80 ° C. and then impregnated with an ammonium fluoride solution, eg preferably under air in a flush bed, eg at 500 ° C. It is possible to start firing for 4 hours.

If the catalyst comprises at least one element of Group VIIA, preferably fluorine, for example impregnating the catalyst with a solution of ammonium fluoride and initiating its drying, for example at 80 ° C., for example preferably Flash floor under air, eg 500 ° C
It is possible to start firing it for 4 hours.

[0053]   Other continuous impregnation steps may be used to obtain the catalyst of the present invention.

If the catalyst contains phosphorus, it is possible, for example, to impregnate the catalyst with a solution containing phosphorus, dry it and then calcine it.

An element contained in the catalyst, ie a metal of group VIII and group VIB, optionally at least one metal selected from the group consisting of boron, silicon and phosphorus,
If at least one element of group VIIA and at least one element of group VIIB are introduced by impregnation of some of the corresponding precursor salts, an intermediate drying step of the catalyst is generally between 60 and 250. It is generally carried out at temperatures of ° C and the intermediate calcination step of the catalyst is generally carried out at temperatures of 250-600 ° C.

To complete the preparation of the catalyst, the wet solids are placed under a humid atmosphere at a temperature of 10-80 ° C. The wet solid obtained is then dried at a temperature of 60-150 ° C. and finally
The obtained solid is calcined at a temperature of 150 to 800 ° C.

Sources of Group VIB elements that can be used are known to those skilled in the art. For example, as molybdenum and tungsten sources, oxides and hydroxides, molybdic acid and tungstic acid and their salts, especially ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid and phosphotungsten phosphide. It is possible to use acids and their salts, silicomolybdic acid and silicotungstic acid and their salts. Ammonium oxides and salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate are preferably used.

Sources of Group VIII elements that can be used are known to those skilled in the art. For example, with respect to non-noble metals, nitrates, sulphates, phosphates, halides such as chlorides, bromides and fluorides, and carboxylates such as acetates and carbonates are used. For noble metals, halides are used. Examples are chlorides, nitrates, acids such as chloroplatinic acid, and oxychlorides such as ruthenium ammoniacal oxychloride.

A preferred phosphorus source is H ₃ PO ₄ orthophosphoric acid, but its salts and esters such as ammonium phosphate are also suitable. Phosphorus may be introduced, for example, in the form of a mixture of phosphoric acid and nitrogen-containing basic organic compounds such as ammonia, primary and secondary amines, cyclic amines, pyridine group compounds and quinoline and pyrrole group compounds. .

Multiple sources of silicon may be used. Therefore, ethyl orthosilicate Si (
OEt) ₄ , siloxane, polysiloxane, ammonium fluorosilicate (
NH ₄₎ It is possible to use _two halide silicates such as SiF ₆ or sodium fluorosilicate Na ₂ SiF _6. Silicomolybdic acid and its salts, and silicotungstic acid and its salts may also be used advantageously. Silicon may be added, for example, by impregnating ethyl silicate in solution in a water / alcohol mixture. Silicon may be added, for example, by impregnating a silicone type silicon compound suspended in water.

The boron source may be boric acid, preferably orthoboric acid H ₃ BO ₃ , ammonium salts of boric acid such as ammonium viborate or ammonium pentaborate, boron oxides and boron esters. Boron is, for example, boric acid,
In the form of a mixture of hydrogen peroxide water and basic organic compounds containing ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine family and nitrogen of the quinolines and pyrrole family of compounds. It may be introduced.

Boron may be introduced, for example, by boric acid solution in a water / alcohol mixture.

Sources of Group VIIA elements that can be used are known to those skilled in the art. For example, the fluoride anion may be introduced in hydrofluoric acid, or salt form thereof. These salts are
Formed with alkali metals, ammonium or organic compounds. In the latter case,
The salt is preferably formed in the reaction mixture by reaction of the organic compound with hydrofluoric acid. Ammonium fluorosilicate _{(NH 4)} 2 SiF _6, such as Tetorafu' of silicon SiF ₄ or sodium fluorosilicate Na ₂ SiF _6, it is also possible to use a hydrolyzable compound capable of releasing fluoride anions in water. Fluorine may be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.

Sources of Group VIIB elements that can be used are known to those skilled in the art. Ammonium salts, nitrates and chlorides are preferably used.

The catalyst thus obtained may be in the oxide form, optionally in at least part of the metal or sulphide form.

The catalysts obtained according to the invention are shaped into granules of different shapes and sizes. They are commonly used in the form of straight or twisted, bilobal, trilobal, multilobal extrudates such as circular or multilobal extrudates, although they are sometimes ground powders, It may be manufactured and used in the form of tablets, rings, beads and rings. They are based on the BET method (Brunauer, Emmett,
Teller, J. Am. Chem. Soc., 60, 308-316 (1938)) specific surface area of 50-600 m ² / g measured by nitrogen adsorption capacity and pore volume measured by mercury porosimeter. It has a pore size distribution of 0.2-1.5 cm ³ / g and may be single peak mode, double peak mode or multiple peak mode.

The catalysts thus obtained are used for the hydroconversion of hydrocarbon feeds (in the broad sense of the conversion in the presence of hydrogen), in particular for hydrocracking and hydrorefining. Therefore, the hydroconversion catalyst contains at least one hydro-dehydrogenating element.

The catalysts obtained according to the invention are used in hydrocracking hydrocarbon feeds such as petroleum fractions. The feedstock used in this method is gasoline, kerosene, gas oil, vacuum gas oil, atmospheric residue, vacuum residue, atmospheric fraction, vacuum fraction, heavy oil, oil, wax and paraffins, used oil, Residual or deasphalted crude oil, and feedstocks and mixtures thereof obtained by heat or catalytic conversion processes. They contain heteroatoms such as sulphur, oxygen and nitrogen and optionally metals.

The catalysts thus obtained are preferably used for hydrocracking, in particular heavy hydrocarbon fractions of the vacuum cut type, deasphalting residues or hydrotreated residues, or their equivalents. The heavy fraction preferably consists of at least 80% by volume of a compound having a boiling point of at least 350 ° C, preferably 350-580 ° C (ie corresponding to a compound containing at least 15-20 carbon atoms). They generally contain heteroatoms such as sulfur and nitrogen. The nitrogen content is usually 1 to 5000 ppm by weight and the sulfur content is 0.01 to 5% by weight.

Hydrocracking conditions such as temperature, pressure, hydrogen recycle rate and hourly space velocity can vary greatly based on feed type, desired material quality and equipment used by refiners. Is. The temperature is generally higher than 200 ° C, often 250-450 ° C. The pressure is greater than 0.1 MPa and often greater than 1 MPa. The hydrogen recycle rate is at least 50 standard liters of hydrogen per liter of feed and in most cases 80 to 5000 standard liters of hydrogen. The hourly space velocity is generally 0.1 to 20 volumes of feedstock per volume of catalyst per hour.

The catalysts of the invention are preferably subjected to a sulfidation treatment which makes it possible to convert at least part of the metallic radicals to sulfides before contacting the catalyst with the feed to be treated. This activation treatment by sulfurization may be carried out by any method known to the person skilled in the art and already described in the literature.

Standard sulphurization processes known to the person skilled in the art generally consist of heating to a temperature of 150 to 800 ° C., preferably 250 to 600 ° C. in the presence of hydrogen sulphide in the flash bed reaction zone.

The catalysts of the invention may be used for the hydrocracking of vacuum cut fractions which are advantageously rich in sulfur and nitrogen. The desired substances are middle distillates and / or middle oils. Advantageously, hydrocracking is used in combination with a prehydrotreating step in the process in the improved production of middle distillates with the production of oil bases having a viscosity index of 95-150.

First implementation of partial hydrocracking, also called mild hydrocracking
In form, the conversion level is less than 55%. Therefore, the catalyst according to the invention is generally above 230 ° C., preferably above 300 ° C., generally at most 480 ° C.,
Often used at temperatures of 350-450 ° C. The pressure is generally greater than 2 MPa, preferably greater than or equal to 3 MPa and less than 12 MPa, preferably 1
It is less than 0 MPa. The amount of hydrogen is at least 10 hydrogen per liter of the feedstock.
0 standard liters, and in most cases 200 to 3000 standard liters of hydrogen per liter of raw material. The hourly space velocity is generally 0.1 to 10 h ^-1 . Under these conditions, the catalyst of the present invention has superior activity in conversion, hydrodesulfurization and hydrodenitrification than commercial catalysts.

In a second embodiment mode, the method is carried out in two steps. Thereby, the catalysts according to the invention are advantageously used for partial hydrocracking under moderate hydrogen pressure conditions, for example of previously hydrotreated, vacuum-distillate fractions rich in sulfur and nitrogen. In this hydrocracking mode, the conversion level is 55%
Is less than. In this case, the petroleum fraction conversion process is carried out in two steps. Therefore, the catalyst according to the invention is used in the second step. The first stage catalyst may be any hydrotreating catalyst included in the prior art. The hydrotreating catalyst advantageously comprises an alumina-based matrix, preferably, and at least one metal having a hydrogenating function. The hydrotreating function is ensured by one or a combination of at least one metal or metal compound selected from Group VIII and Group VIB metals, in particular selected from nickel, cobalt, molybdenum and tungsten. In addition, the catalyst may optionally include phosphorus and optionally boron.

The first step is generally at a temperature of 350 to 460 ° C., preferably 360 to 450 ° C., an overall pressure of at least 2 MPa, preferably at least 3 MPa and an hourly space velocity of 0.
^{1 to 5} h ^-1 , preferably 0.2 to 2 h ^-1 , hydrogen amount of at least 100 NL / feeding material NL (standard liter), preferably 260 to 3000 NL / feeding material NL
Done in.

[0077]   In the conversion step (or second step) using the catalyst according to the present invention, the temperature is
Generally 230 ° C or higher, often 300-480 ° C, preferably 330-450
℃. The pressure is generally at least 2 MPa, preferably at least 3 MPa
And less than 12 MPa, preferably less than 10 MPa. The amount of hydrogen is
At least 100 L of hydrogen per liter of feedstock / L of feedstock, often 20
0 to 3000 L / charged raw material L. The hourly space velocity is generally 0.15 to 10 h. ^-1 Is. Under these conditions, the catalyst of the present invention is in the middle distillate a commercial catalyst.
With excellent activity in rimo conversion, hydrodesulfurization and hydrodenitrification, and excellent selectivity
Have. The life of the catalyst is also improved in the moderate pressure range.

In another two step embodiment, the catalyst of the present invention is at least 5 MP
It may be used for hydrocracking under high hydrogen pressure conditions of a. The treated fraction is, for example, a prehydrotreated, distillate type rich in sulfur and nitrogen. In this hydrocracking mode, conversion levels are above 55%.
In this case, the petroleum fraction conversion method is carried out in two steps. Therefore, the catalyst according to the invention is used in the second step.

The first stage catalyst may be any hydrotreating catalyst included in the prior art. The hydrotreating catalyst advantageously comprises an alumina-based matrix, preferably, and at least one metal having a hydrogenating function. The hydrotreating function may be a primary one, especially selected from nickel, cobalt, molybdenum and tungsten.
Reserved by at least one metal or metal compound selected from Group VIII and Group VIB metals, alone or in combination. In addition, the catalyst may optionally include phosphorus and optionally boron.

[0080]   The first step is generally at a temperature of 350 to 460 ° C, preferably 360 to 450 ° C, 3
Pressure over MPa, hourly space velocity 0.1-5h^-1, Preferably 0.2 to 2 h ^-1 , Hydrogen amount of at least 100 NL / feeding material NL (standard liter), preferably
Is carried out at 260 to 3000 NL / charged raw material NL.

In the conversion step (or second step) using the catalyst according to the present invention, the temperature is
Generally 230 ° C or higher, often 300-480 ° C, preferably 300-440
℃. The pressure is generally greater than 5 MPa, preferably greater than 7 MPa. The amount of hydrogen is at least 100 L of hydrogen / liter of charged material per liter of charged material,
In many cases, it is 200 to 3000 L / feeding material L. Hourly space velocity is generally 0
． It is 15 to 10 h ^-1 .

Under these conditions, the catalysts of the present invention show better conversion activity of middle distillates and better selectivity than commercial catalysts, even at zeolite contents much lower than those of commercial catalysts. Have.

In the process for the production of oil, which advantageously uses the hydrocracking process according to the invention, the operation reaches an effluent with a viscosity index of 90 to 130 and a reduced content of nitrogen and polyaromatic compounds. It is carried out in accordance with the teaching of US Pat. No. 5,525,209 using a first hydrotreating step under conditions that allow In the next hydrocracking step, the effluent is treated according to the invention to adjust the value of the viscosity index to the value desired by the user.

The catalysts obtained according to the invention are also used for hydrorefining hydrocarbon feeds such as petroleum fractions (fractions obtained from carbon or hydrocarbons originating from natural gas). The main reactions used are the hydrogenation, hydrodenitrification, hydrodeoxygenation, hydrodesulfurization and hydrodemetallation of aromatic compounds, most often with hydrocracking. The hydrocarbon feedstock comprises aromatic compounds and / or olefinic compounds and / or naphthenic compounds and / or paraffinic compounds, optionally metals and / or nitrogen and / or oxygen and / or sulfur. In these uses, the catalysts obtained according to the invention have improved activity compared to the prior art.

The feed materials used in this method are gasoline, gas oil, vacuum gas oil, atmospheric residue, vacuum residue, atmospheric fraction, vacuum fraction, heavy oil, oil, wax and paraffins, used oil. , A deasphalted residue or crude oil, and a feedstock and a mixture thereof obtained by a heat conversion method or a catalytic conversion method. They contain heteroatoms such as sulfur, oxygen and nitrogen and at least one metal. Non-limiting examples of heavy fractions are vacuum cuts, deasphalting residues or hydrotreated residues or equivalents thereof, preferably with a boiling point of at least 350.
It comprises at least 80% by volume of the compound having a temperature of 350C, preferably 350-580C (ie corresponding to a compound containing at least 15-20 carbon atoms). They generally contain heteroatoms such as sulfur and nitrogen. Nitrogen content is usually 1
-5000 ppm by weight and the sulfur content is 0.01-5% by weight.

The catalysts of the invention are also preferably used during the pretreatment of the catalytic cracking feed, preferably in the first step of mild hydrocracking or hydroconversion. They are then usually used in combination with zeolitic or non-zeolitic acid catalysts in the second treatment step.

Hydrorefining conditions such as temperature, pressure, hydrogen recycle rate and hourly space velocity are:
They are very diverse based on the type of feedstock, the quality of the desired material and the equipment used by the refiner. Temperatures are generally higher than 200 ° C, often 2
It is 50-480 degreeC. Pressure is greater than 0.05MPa, often 1MP
greater than a. The hydrogen recycle rate should be at least 8 hydrogen per liter of feedstock.
0 standard liters, often 50-5000 standard liters of hydrogen. The hourly space velocity is generally 0.1 to 20 volumes of feedstock per volume of catalyst per hour.

The catalysts of the present invention are preferably subjected to a sulfidation treatment which may convert at least part of the metallic radicals to sulfides before contacting the catalyst with the feed to be treated. This activation treatment by sulfurization may be carried out by any method known to the person skilled in the art and already described in the literature.

Standard sulphurization processes known to the person skilled in the art are the solid sulphides, generally in a flash bed reaction zone under a mixed stream of hydrogen and hydrogen sulphide or a mixture of nitrogen and hydrogen sulphide at a temperature of 150-800 ° C., preferably 250-800 ° C. Consists of heating at 600 ° C.

Important results for refiners are HDS activity, HDN activity and conversion activity. The intended goal must be achieved under conditions compatible with achieving economic savings. Therefore, refiners strive to reduce temperature, pressure and hydrogen recycle rates to maximize hourly space velocities. Although activity can be increased by increasing the temperature, it is known to often sacrifice catalyst stability.
This stability or life is improved with increasing pressure or hydrogen recycle rate, at the expense of economic savings in the process.

[0091]

DETAILED DESCRIPTION OF THE INVENTION

  The following examples illustrate the invention but do not limit its scope.

Example 1: Preparation of hydrocracking or hydrorefining catalyst support containing partially amorphous zeolite Y Overall Si / Al molar ratio 15.2, Si / Al skeleton ratio 29, and crystal parameters 24 .29Å, 0.03 wt% Na, 0.48 peak ratio, 85% of the crystalline ultra-stable dealuminated zeolite USY with a partial vapor pressure of 0.5 absolute bar. It was then amorphized by hydrothermal treatment at 620 ° C. for 5 hours. The zeolite was then subjected to acid attack under the following conditions. That is, the acid normality was 0.85 N, the period was 3 hours, and the temperature was 95 ° C. A final hydrothermal treatment identical to the first hydrothermal treatment with a partial pressure of steam of 0.02 bar was applied to the zeolite. At the end of these treatments, the partially amorphous zeolite has a peak ratio of 0.26, a crystalline portion of 44%, an overall Si / Al ratio of 72, a Si / Al ^iv skeleton ratio of 80, and liquid nitrogen It had a pore volume of 0.35 ml, of which 29% consisted of pores with a diameter of at least 5 nanometers (50 Å). A hydrocracking catalyst support containing this zeolite Y was produced as follows.

60 g of the above-described partially amorphous zeolite Y was added to ultra-thin plate-like boehmite or
It was mixed with 40 g of a matrix consisting of an alumina gel marketed under the trade name SB3 by the company Condea Chemie GmbH. The powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight acid per gram dry gel) and then kneaded for 15 minutes. At the end of this kneading, the paste obtained was passed through a die having a cylindrical hole mouth with a diameter of 1.4 mm. The extrudates were then dried under air at 120 ° C overnight and then calcined under air at 550 ° C.

Example 2 Preparation of Hydrocracking or Hydrorefining Catalyst Containing Partial Amorphous Zeolite Y According to the Present Invention A carrier extrudate containing partial amorphous zeolite Y of Example 1 was treated with heptamolybdenum. It was dry impregnated with an aqueous solution of ammonium acidate, dried under air at 120 ° C. overnight and finally calcined under air at 550 ° C. The weight content of the obtained Y ₁ Mo catalyst oxide is shown in Table 1.

The Y ₁ Mo catalyst was then impregnated with an aqueous solution containing ammonium viborate in order to obtain a loading of about 1.7% by weight of B ₂ O ₃ . After aging at room temperature under a saturated atmosphere of water, the impregnated extrudates were dried at 120 ° C. overnight and then calcined under dry air at 550 ° C. for 2 hours. A catalyst designated Y ₁ MoB was obtained. Then, similarly, a Y ₁ MoSi catalyst was added to Rhodorsi to support about 2.0% of SiO _2.
Prepared by impregnation of Y ₁ Mo catalyst with EP1 silicone emulsion (Rhone Poulin). The impregnated extrudate is then dried at 120 ° C. overnight,
They were then calcined under dry air at 550 ° C. for 2 hours. Finally, Y ₁ MoBS
i catalyst is ammonium viborate and Rhodorsil EP1 (Rhone Poulin)
This was accomplished by impregnation of the Y ₁ Mo catalyst with an aqueous solution containing a silicone emulsion. The impregnated extrudates were then dried overnight at 120 ° C and then calcined under dry air at 550 ° C for 2 hours.

The carrier extrudate containing the partially amorphous zeolite Y prepared in Example 1 is dry impregnated with an aqueous solution of a mixture of ammonium heptamolybdate and nickel nitrate and dried under air at 120 ° C. overnight. And then calcined at 550 ° C. in air. Table 3 shows the weight content of the obtained Y ₁ NiMo catalyst oxide.

The extrudates were dry impregnated with an aqueous solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, dried under air at 120 ° C. overnight and finally calcined under air at 550 ° C. The weight content of the resulting Y ₁ NiMoP catalyst oxide is shown in Table 3.

A sample of Y ₁ NiMoP catalyst was then impregnated with an aqueous solution containing ammonium viborate. After aging at room temperature under a saturated atmosphere of water, the impregnated extrudates were dried at 120 ° C. overnight and then calcined under dry air at 550 ° C. for 2 hours.
A catalyst designated Y ₁ NiMoPB was obtained.

The Y ₁ NiMoPSi catalyst was obtained by the same procedure as the Y ₁ NiMoPB catalyst above, but by replacing the boron precursor with a Rhodorsil EP1 silicone emulsion in the impregnation solution.

Finally, a Y ₁ NiMoPBSi catalyst was obtained by the same procedure as the above catalyst, but using an aqueous solution containing ammonium viborate and Rhodorsil EP1 silicone emulsion. Fluorine was then added to the catalyst by impregnation with a hydrohydrofluoric acid solution diluted to support about 1% by weight fluorine. After drying overnight at 120 ° C. and then calcination in dry air at 550 ° C. for 2 hours, a Y ₁ NiMoPBSSiF catalyst was obtained. The final content of Y ₁ NiMo catalyst oxide is shown in Table 1.

[0101]

[Table 1]

The Y ₁ NiMoP catalyst was then impregnated with an aqueous solution containing manganese nitrate. After aging at room temperature under a saturated atmosphere of water, the impregnated extrudates were dried overnight at 120 ° C and then calcined under dry air at 550 ° C for 2 hours. Y ₁ NiMoPM
A catalyst named n was obtained. The catalyst is then treated with ammonium viborate and Rhod.
It was impregnated with an aqueous solution containing orsil EP1 (Rhone Poulin) silicone emulsion. The impregnated extrudate was then dried at 120 ° C. overnight and then calcined under dry air at 550 ° C. for 2 hours to give a Y ₁ NiMoPMnBSi catalyst.
The diluted hydrofluoric acid solution was then added to the fluorine catalyst by impregnation to support about 1% by weight fluorine. After drying overnight at 120 ° C. and then calcination under dry air at 550 ° C. for 2 hours, a Y ₁ NiMoPMnBSiF catalyst was obtained. The weight content of these catalysts is shown in Table 2.

[0103]

[Table 2]

Y ₁ NiMoPSi catalyst, Y ₁ NiMoP PBSi catalyst and Y ₁ NiMoPB
SiF catalyst (Table 3), Y ₁ NiMoPMnBSi catalyst and Y ₁ NiMoPM
Analysis by electron microprobe with nBSiF catalyst (Table 3b) shows that the silicon added to the catalyst according to the invention is mainly localized on the matrix and is in amorphous silica form.

Example 3 Preparation of Support Containing Y ₁ Zeolite and Silica-Alumina A silica-alumina powder having a composition of 2% SiO ₂ and 98% Al ₂ O ₃ was produced by coprecipitation. Then, a hydrocracking catalyst carrier containing the silica-alumina and the partially amorphous zeolite Y of Example 1 was produced. For this,
50% by weight of the partially amorphous zeolite Y of Example 1 mixed with 50% by weight of the silica-alumina matrix prepared above was used. The powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight acid per gram dry gel) and then kneaded for 15 minutes. At the end of this kneading, the paste obtained was passed through a die having a cylindrical hole mouth with a diameter of 1.4 mm. The extrudate is then placed at 120 ° C.
It was dried overnight at 550 ° C. and then calcined under air at 550 ° C. for 2 hours.

Example 4 Preparation of Hydrocracking Catalyst Containing Partial Amorphous Zeolite Y and Silica-Alumina A carrier extrudate containing silica-alumina and Partial Amorphous Zeolite Y of Example 3 was treated with heptamolybdenum. It was dry impregnated with an aqueous solution of a mixture of ammonium acid salt, nickel nitrate and orthophosphoric acid, dried under air at 120 ° C. overnight and finally calcined under air at 550 ° C. Table 4 shows the weight content of the obtained Y ₁ -SiAl-NiMoP catalyst oxide.

A sample of Y ₁ -SiAl-NiMoP catalyst was impregnated with an aqueous solution containing ammonium viborate to impregnate 1.5% by weight of B ₂ O ₃ . After aging at room temperature under a saturated atmosphere with water, the impregnated extrudates are dried at 120 ° C. overnight,
Then, it was calcined under dry air at 550 ° C. for 2 hours. Therefore, a catalyst named Y ₁ -SiAl-NiMoPB containing silicon in the silica-alumina matrix was obtained. The characteristics of the Y ₁ -SiAl-NiMo catalyst are summarized in Table 3.

[0108]

[Table 3]

Example 5: Preparation of Supports Containing Prior Art Zeolites A hydrocracking catalyst support containing zeolite Y was prepared in large quantities so that various catalysts based on the same support could be prepared. For this, 20.5% by weight of the same commercial zeolite USY was used as the zeolite used in Example 1. This zeolite is a matrix 79.5 consisting of ultra-thin tabular boehmite or an alumina gel marketed under the trade name SB3 by the company Condea Chemie GmbH.
Mixed with wt%. The powder mixture was then mixed with an aqueous solution containing 66% nitric acid (7% by weight acid per gram dry gel) and then kneaded for 15 minutes. At the end of this kneading, the paste obtained was passed through a die having a cylindrical hole mouth with a diameter of 1.4 mm. The extrudate was then dried at 120 ° C overnight and then calcined under air at 550 ° C for 2 hours. A 1.2 mm diameter cylindrical extrudate was obtained with a specific surface area of 223 m ² / g and a single mode pore size distribution centered at 10 nm.

[0110] [Example 6: Preparation method of hydrocracking catalyst containing zeolite Y of Example 5]   A carrier extrudate containing dealuminated zeolite Y of Example 5 was treated with heptamolyb.
With an aqueous solution of a mixture of ammonium denoate, nickel nitrate and orthophosphoric acid.
Dry impregnation, dry overnight in air at 120 ° C, and finally bake in air at 550 ° C
did. The weight content of the obtained YNiMoP catalyst oxide is shown in Table 5. Final YN
iMoP catalysts are especially_Two/ Al_TwoO_ThreeRatio 30.4 and SiO_Two/ Al _Two O_ThreeZeolite Y with unit cell parameter 2.429 nm with skeleton ratio 58
It contained 16.3% by weight.

A sample of YNiMoP catalyst was impregnated with an aqueous solution containing ammonium viborate. After aging at room temperature under a saturated atmosphere of water, the impregnated extrudates were
It was dried overnight at 0 ° C. and then calcined under dry air at 550 ° C. for 2 hours. A NiMoP / alumina-Y catalyst activated with boron was obtained.

The YNiMoPSi catalyst was obtained by the same procedure as the YNiMoPB catalyst above, but substituting the Rhodorsil EP1 (Rhone-Poulin) silicone emulsion for the boron precursor in the impregnation solution.

Finally, YNiMoPBSi catalyst was added with ammonium viborate and Rhodorsil
Achieved by impregnation of the catalyst with an aqueous solution containing EP1 (Rhone Poulin) silicone emulsion. The other steps of the precursor were the same as shown above. The characteristics of the YNiMo catalyst are summarized in Table 4.

[0114]

[Table 4]

Analysis of the YNiMoPSi and YNiMoPBSi catalysts (Table 5) by electron microprobe shows that the silicon added to the catalyst according to the invention is mainly localized on the matrix and in amorphous silica form. It was

Example 7 Comparison of Reduced Pressure Gas Oil Hydrocracking Catalysts Using Partial Conversion A catalyst having the preparation method described in the above example was run at moderate pressure for petroleum feedstocks with the following main characteristics: Used under hydrocracking conditions at: Density (20/4) 0.921 Sulfur (wt%) 2.46 Nitrogen (wt ppm) 1130 Simulated distillation initial boiling point 365 ° C. 10% point 430 ° C. 50% point 472 ℃ 90% point 504 ℃ Final boiling point 539 ℃ Pour point +39 ℃

The catalyst test apparatus comprises two fixed bed reactors with an upflow of feed (“up-flow”). Into the first reactor, which is the reactor through which the feedstock first passes, was introduced the hydrotreating process catalyst HTH548 containing Group VI and Group VIII elements sold by Procatalys and supported on alumina. The above-mentioned hydrocracking catalyst was introduced into the second reactor, which is the reactor through which the charged raw material finally passed.
40 ml of catalyst was introduced into each of the reactors. The two reactors were operated at the same temperature and the same pressure. The operating conditions of the test apparatus were as follows: Total pressure 5 MPa Hydrotreating catalyst 40 cm ³ Hydrocracking catalyst 40 cm ³ Temperature 400 ° C. Hydrogen flow rate 20 l / h Charged material flow rate 40 cm ³ / h

The two catalysts underwent an in-situ sulfidation step prior to reaction. It has been found that any on-site or off-site sulfurization method is suitable. Once sulphurised, the above feeds could be converted.

[0119] The catalytic performance was measured by hydrodesulfurization conversion (HDS) and hydrodenitrification conversion (HDN).
Displayed by These catalytic performances are shown to have a stabilization period of generally at least 48
Measurements were made on the catalyst after a lapse of time.

The hydrodesulfurization conversion HDS is assumed as follows: HDS = (S _initial −S _effluent ) / S _initial × 100 = (24600−S _effluent ) / 24600 × 100

The hydrodenitrification conversion rate HDN is assumed as follows: HDN = (N _initial −N _effluent ) / N _initial × 100 = (1130−N _effluent ) / 1130 × 100

In the table below, the hydrodesulfurization conversion rate (HDS) and hydrodenitrification conversion rate (H
DN) and

[0123]

[Table 5]

The results in Table 6 show that the use of the catalyst according to the invention with partially amorphous zeolite Y is more active in hydrodesulfurization and hydrodenitrification than the prior art catalysts. In contrast, the addition of at least one element selected from the group consisting of B, Si and P led to an improvement in the performance level of the catalyst according to the invention.

In addition, the results in Table 6 show that the catalysts already prepared (Y ₁ rather than the introduction of silicon into the silicon-containing support (Y ₁ -SiAl-NiMo series) form obtained from silica-alumina. NiMo) has been shown to be advantageous. It is therefore particularly advantageous to introduce silicon into a precursor which already contains an element of group VIB and / or VIII and optionally at least one element of element P, element B and element F. there were.

Example 8: Comparison of catalysts in hydrocracking of high conversion vacuum gas oils [0126] Catalysts with the preparation methods described in the previous examples were subjected to high conversion hydrocracking conditions (60-100%). used. The petroleum feed was a hydrotreated vacuum cut having the following main characteristics:

[0127] Density (20/4) 0.869 Sulfur (ppm by weight) 502      Nitrogen (weight ppm) 10 Simulation distillation Initial boiling point 298 ℃ 10% point 369 ° C 50% point 427 ° C 90% point 481 ° C Final boiling point 538 ℃

This feed was obtained by hydrotreating a vacuum cut over an HR360 catalyst sold by Pro-Catalyse Company and supported on alumina containing Group VIB and Group VIII elements.

H ₂ S precursor sulfur-containing compounds and NH ₃ precursor nitrogen-containing compounds were treated with hydrotreated hydrocarbons to simulate the partial pressure of H ₂ S and NH ₃ present in the _second hydrocracking step. Was added to. The feedstock thus prepared was injected into a hydrocracking test apparatus equipped with a fixed bed reactor having an upflow (“up-flow”) of the feedstock into which 80 ml of catalyst was introduced. Prior to injecting the charge, the catalyst was sulphided to 320 ° C. with n-hexane / DMDS + aniline mixture. It has been found that any on-site or off-site sulfurization method is suitable. Once sulphurised, the above feeds could be converted. The operating conditions of the test equipment were as follows.

Total pressure 9 MPa Catalyst 80 cm ³ Temperature 360 to 420 ° C. Hydrogen flow rate 80 l / h Charged material flow rate 80 cm ³ / h

The catalyst performance is 150-380 at a temperature at which a rough conversion level of 70% can be reached.
C. and the crude selectivity of middle distillates. These catalytic performances were measured on the catalyst after a stabilization period of generally at least 48 hours had elapsed.

The approximate conversion CB is assumed as follows: CB =% by weight of the effluent below 380 ° C. The crude selectivity SB of middle distillates is assumed as follows: SB = 100 × Weight of fraction (150-380 ° C) / 380 ° C of effluent
Weight of less than fractions The middle distillates obtained consisted of substances having a boiling point of 150-380 ° C.

The reaction temperature was set to reach an approximate conversion CB of 70% by weight. Table 6 below records the reaction temperatures, the crude selectivities for the catalysts listed in Tables 3 and 3b, and the viscosity index values measured in the 380 ° C. ⁺ fraction after removal of paraffins in the solvent.

Table 6 shows that the use of the catalysts according to the invention comprising partially amorphous zeolite Y leads to higher middle cut crude selectivities than those of the prior art anomalous catalysts. On the other hand, at least 1 selected from the group consisting of P, B and Si
The addition of two elements to the catalyst according to the invention also led to an increase in activity. An improvement in activity brought about by the presence of manganese or fluorine was also observed.

In addition, it became clear that the viscosity index of the 380 ° C. ⁺ fractions obtained with the catalyst according to the invention is clearly improved.

In general, conversion activity is obtained by adding at least one element selected from P, B, Si, groups VIIB and VIIA to a catalyst comprising partially amorphous zeolite Y and a group VIB element. It has become possible to improve. This was brought about by the reduction in reaction temperature required to reach a conversion of 70%.

[0137]

[Table 6]

[Example 9: Hydrotreatment test of reduced pressure cut] Y ₁ NiMo catalyst, Y ₁ NiMoP catalyst, and Y ₁ NiMo having the above-mentioned preparation method
PB catalysts, Y ₁ NiMoPBSi catalysts and Y ₁ NiMoPBSiF catalysts were compared in a vacuum cut hydrotreatment test with the main characteristics provided in the following table: Density at 15 ° C. 0.938 Sulfur 3.12 Weight% Total nitrogen 1050 weight ppm Simulation initial distillation point 345 ° C 10% point 412 ° C 50% point 488 ° C 90% point 564 ° C Final boiling point 615 ° C

The test was conducted in an isothermal pilot reactor with a flash fixed bed.
Therefore, the fluid circulated in the ascending direction. After in-situ sulphurization at 350 ° C., hydrotreatment tests were carried out under the following operating conditions in a pressurizer using straight run gas oil supplemented with 2% by weight of dimethyl disulfide: Total pressure 12 MPa Catalyst volume 40 cm ³ Temperature 380 ° C. Hydrogen flow rate 24 l / h Charged material flow rate 20 cm ³ / h

The catalyst performance levels of the tested catalysts are shown in Table 7 below. Let them be Y ₁ NiM
o The relative activity was expressed by assuming that the activity of the catalysts was 1, and by considering them to be around 1.5. Activity and hydrodesulfurization conversion rate (
The expression relating to (HDS%) is as follows.

[0141]

[Formula 1]

The same formula was applicable for _{hydrodenitrification} (% HDN and A _HDN ).

The net conversion of the feed fraction (380 ° C. ⁺ wt%) having a boiling point higher than 380 ° C. obtained with each catalyst was also evaluated. It is shown by the following formula, starting from the simulated distillation result (ASTM D86 method).

[0144]

[Formula 2]

[0145]

[Table 7]

These examples make it possible to achieve higher activities in hydrodesulfurization and hydrodenitrification and net conversions than the catalysts known from the prior art at 380 ° C. ^- substance (
All the advantages in the use of the catalyst according to the invention made possible in substances having a boiling point below 380 ° C. have been shown.

The catalysts according to the invention thus have a high degree of activity in the hydrogenation, hydrodenitrification and hydrodesulfurization of aromatic hydrocarbons. Although not supported by theory,
The particularly high activity of the catalysts of the present invention was believed to be due to the presence of the amorphized zeolite. It was reinforced by the presence of covalent boron and silicon on the matrix, which on the one hand resulted in improved hydrogenation, hydrodesulfurization and hydrodenitrification properties and, on the other hand, improved conversion.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] May 23, 2001 (2001.5.23)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Contents of correction]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 12

[Correction method] Change

[Contents of correction]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 14

[Correction method] Change

[Contents of correction]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Contents of correction]

Y ₁ NiMoPSi catalyst, Y ₁ NiMoP PBSi catalyst and Y ₁ NiMoPB
SiF catalyst (Table 1 ), Y ₁ NiMoPMnBSi catalyst and Y ₁ NiMoPM
Analysis by electron microprobe with nBSiF catalyst (Table 2 ) shows that the silicon added to the catalyst according to the invention is mainly localized on the matrix and is in amorphous silica form.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Contents of correction]

Example 4 Preparation of Hydrocracking Catalyst Containing Partial Amorphous Zeolite Y and Silica-Alumina A carrier extrudate containing silica-alumina and Partial Amorphous Zeolite Y of Example 3 was treated with heptamolybdenum. It was dry impregnated with an aqueous solution of a mixture of ammonium acid salt, nickel nitrate and orthophosphoric acid, dried under air at 120 ° C. overnight and finally calcined under air at 550 ° C. Table 3 shows the weight content of the obtained Y ₁ -SiAl-NiMoP catalyst oxide.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Contents of correction]

Analysis of the YNiMoPSi catalyst and the YNiMoPBSi catalyst (Table 4 ) by electron microprobe shows that the silicon added to the catalyst according to the invention is mainly localized on the matrix and is in amorphous silica form. It was

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Contents of correction]

The reaction temperature was set to reach an approximate conversion CB of 70% by weight. In Table 6 below, the reaction temperatures, the crude selectivities for the catalysts listed in Tables 1 and 2 and the viscosity index values measured in the 380 ° C. ⁺ fraction after removal of paraffins in the solvent are recorded.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), BR, IN, J P, KR, SG (72) Inventor Le Bourg Bernadette             France Elmon Plus de la               Grand Tour 1 (72) Inventor Chenu Frederick             France Beauvoir sur             Email Rudes The Turn 30 (72) Inventor Kuzli Chivadar             Courbevoie Terrace des France             Rufflet 5 (72) Inventor Kazturan Slavik             France Ril Malmaison Ryu             Knot 27 F-term (reference) 4G069 AA03 BA01A BA01B BA02A                       BA02B BA03A BA03B BA07A                       BA07B BB01A BB01B BB04A                       BB04B BB06A BC16A BC57A                       BC59A BC59B BC60A BC61A                       BC62A BC62B BC65A BC66A                       BC67A BC68A BC68B BC69A                       BC70A BC71A BC72A BC73A                       BC74A BC75A BD02A BD02B                       BD03A BD03B BD05A BD07A                       BD07B BD11A BD15A BD15B                       CC02 CC04 CC05 EC03X                       EC03Y EC04X EC04Y EC06X                       EC06Y EC14X EC14Y EC26                       EC29 FC08 ZA04A ZA05B                       ZC01 ZC04 ZC07 ZD01 ZD03                       ZD04 ZE05 ZF02A ZF02B                       ZF05A ZF05B                 4H029 CA00 DA00

Claims (24)

[Claims] 1. At least one matrix and at least one partial fraction having a peak fraction of less than 0.4 and less than 60% of the crystalline portion expressed relative to a reference zeolite in the sodium (Na) form. A catalyst containing crystalline zeolite Y. 2. The method according to claim 1, further comprising at least one hydrogenation / dehydrogenation element.
The described catalyst. 3. The zeolite has the following further characteristics: -total Si / Al ratio greater than 15; -Si / Al ^IV framework ratio above the total Si / Al ratio; -fineness at least equal to 0.20 ml / g of solids. 3. Catalyst according to claim 1 or 2, characterized in that it has at least one of a pore volume (8-50% of which consists of pores having a diameter of at least 5 nm) and a specific surface area of 210-800 m < ² > / g. . 4. The catalyst according to claim 2, wherein the hydrogenation / dehydrogenation element is selected from Group VIII elements and Group VIB elements. 5. The catalyst according to claim 1, containing at least one element selected from the group consisting of phosphorus, boron and silicon. 6. The catalyst according to claim 5, wherein the element is supported on the catalyst and is mainly localized on the matrix. 7. The method of claim 1 further comprising at least one Group VIIA element.
6. The catalyst according to any one of 6 above. 8. The method of claim 1 further comprising at least one element of Group VIIB.
7. The catalyst according to any one of 7. 9. The catalyst according to claim 8, wherein the Group VIIB element is manganese. 10. At least one oxide-type amorphous or incompletely crystallized porous inorganic matrix, in an amount of 0.1 to 99.9% by weight, based on the total weight of the catalyst; Crystalline zeolite Y 0.1 to 99.9%, at least one hydrogenation / dehydrogenation element 0 to 60%, at least one element 0 to 2 selected from the group consisting of boron, silicon and phosphorus
0%, at least one element from Group VIIA 0-20%, and at least one element from Group VIIB 0-20%, according to any one of claims 1-9. catalyst. 11. A catalyst according to claim 1, wherein the matrix is selected from alumina, silica-alumina, aluminates and silica. 12. The catalyst according to claim 1, wherein the partially amorphous zeolite Y is obtained by applying dealumination technology on a commercially available zeolite Y. 13. The catalyst according to claim 12, wherein the technique is used in a combination of hydrothermal treatment, ion exchange and acid attack. 14. At least one partially amorphous zeolite Y having at least one matrix and a peak fraction of less than 0.4 and less than 60% of the crystalline portion displayed relative to a reference zeolite in the sodium (Na) form. And a method for hydroconversion of a hydrocarbon feedstock, which further comprises a catalyst containing at least one hydrogenation / dehydrogenation element. 15. The method of claim 14 which is hydrocracking. 16. A method according to claim 1, wherein the temperature is over 200 ° C., the pressure is over 0.1 MPa, the space velocity is 0.1-20 h ⁻¹ , and the hydrogen recycle rate is at least 50 standard liters (Nl) / 1 liter of the feedstock. 15. The method for hydrocracking according to 15. 17. The pressure is above 2 MPa and below 12 MPa, the temperature is at least 230 ° C., the space velocity is 0.1 to 10 h ⁻¹ , and the hydrogen recycle rate is at least 100 Nl / charge. 16. The method according to claim 15, wherein the raw material is 1 liter, whereby the conversion rate is less than 55%. 18. The method of claim 15, wherein the pressure is at least 5 MP and the conversion is greater than 55%. 19. The method according to claim 15, wherein the catalyst is pre-sulphurized. 20. The method of any one of claims 15-18, wherein the feedstock is hydrotreated before being hydrocracked. 21. The method of claim 14, which is hydrorefining. 22. Operating at a temperature above 200 ° C., a pressure above 0.05 MPa, a hydrogen recycle rate of at least 80 Nl / liter of feed, and an hourly space velocity of 0.1 to 20 h ^−1. The method described. 23. The method of claim 21, wherein the catalyst is pre-sulfided. 24. A process according to claim 14, which is operated with a catalyst according to any one of claims 3 to 13.